Coloring of cellulose derivatives



lPatented Aug, H6, 1932 unit-en stares GEORGE HOLLAND ELLIS AND HENRY CHARLES ClLlPIN, 01E SJPCNDUN, NEAR DERBY, ENGLAND, ASSIGNOR 'lO CELANESE CORPORATION (OF AMERICA, A CQRPOBATION F DELAWARE COLORING- QF CELL-CLOSE DERIVATIVES No Drawing. Application filed. September 22, 1928, Serial No. 307,771, and in Great Britain November This invention relates to dyeing, printing, stencilling or otherwise coloring yarns, threads, fabrics or other products made with or containing cellulose acetate or other organic acid esters of cellulose, for'instance cellulose formate, propionate or butyrate or the products obtained by the treatment of alkalized cellulose with esterifying agents (e. g. the product known as immunized cotton made with p-toluene sulphochloride), or made with or containing celluloseethers, for. example methyl, ethyl or benzyl cellulose, or the corresponding condensation products of cellulose and glycols or other polyhydric' al oohols. All such cellulose derivatives are hereinafter referred to as organic substitu- I tion derivatives of cellulose.

According to the present invention materials made with or containing celluloseacetate or other organic substitution derivatives of cellulose are dyed or otherwise'colored with unsulphonated thiazole derivatives, i. e. coloring matters or compounds containing the group D N ble of eitectiin a coupling may be similarly developed by means of diazo-bodies.

The dyestuffs or components may be applied to the fibre in any suitable form. They are usually insufficiently soluble in water and, to apply, them from an aqueous medium, they may be suspended or dispersed by any convenient methods. For example they may be dispersed by milling (e. g. in the so-called colloid mills) or by dissolving in a solvent and mixing the solution with water containing or not containing a protective colloid or they may be dispersed with the aid of dispersators for instance by the methods described in British Patent No. 219,349 corresponding to U. S. Patent No. 1,618,413, British Patent No. 224,925 corresponding to U. S. Patent No. ,1,618,41d, British Patent No 242,393 corresponding to U. S. Patent No. 1,694,413, -British Patent No. 242,711 corresponding to U. S. Patent No. 1,690,481 and in British Patents Nos. 269,960, 273,819 and 273,820..

The following examples of dyestufis applied in substance and of dyestufi's produced on the fibre are intended to illustrate but not to limit the invention A. Dyestufis applied in substance from aqueous dispersions.

(1) Compound obtained by diazotizing I dehydrothio-p-toluidine and coupling, 7

with phenol having the probable formula '1 lir -0 0 gives a yellow shade. (2) Compound obtained by diazotizing dehydrothio-p-toluidine and coupling with m-toluylenediamine having the probable formula:

' N Gila-O S CH: 7 (b -O f) H K Com und obtained by condensing with 2.5-dichlornitrobenzene having the probable formula: a I No 7o glves a yellow shade. 34 Comgound 'obtalned by condensmg 0 e ydrot Tlo-p-toluidme wlth 2.4-din1- on s trochlorbenzene having the probable v 1o formula:

. I N01 ves a ellow shade. N\ B. yestu s formed on the fibre. CH O Cellulose acetate is first dyed wlth dehy- 7 N0: drothio-p-toluidine from an aqueous disll v perslon, the dyemgdlazotized and de- 'ves a ellow shade. velo d withthefollowin develo ers:- g y P g P Develpel Probable formula of dye Shade 20 N Phenol '0 CON= OOH Yellow 0H e as v 00 am on B so I DlmethYlc V N on aniline I CH N Orange N d-naDh- CON=N thylamlne CH a) 5:332 a I 10;

N y c- N=N- fl-naphthol CH 8 H0 glgmge o N=N-- lififififi'fiic CH 5 Hm- B ed acid wr- 5 HOOC- l-napihntngb CH1 9 0 am 55 th B d 2m e ethyl-v naphthyl- Red amine Developer Probable formula of dye Shade naphthyl- CH S cs t N Red amine 2.3-11 droxynaghthoic BLO filgish acid Though in the above examples dehydrothio- *p-toluidine has alone been employed asxthe thiazole derivative, it is to be regarded as merely typical of the compounds which may be employed according to the invention. 1

The invention further comprises the dyeing or otherwise coloring of mixed goods containing, for example, in addition to the cellulose ester or ether, wool, silk, cotton or artificial silks or fibres of the cellulosic type, other dyestuiis being applied, if desired, to the nonester or non-ether portion. either before, after, or, it compatible, together with the dyestufls of the present invention.

The following examples illustrate the production of colorations according to the present invention, but are not to be considered as limiting its scope in any way Eacample I of cold soft water, the goods entered, and the temperature raised during hr. to 580 C. and maintained at this temperature until the desired shade is achieved. The fabric is then lifted, rinsed and dried or otherwise as requisite.

Ewample l I To dye a yellow shade on 10 kilos of cellulose acetate knit fabric 1 kilo of a 10% aqueous paste of the dyestufi obtained by coupling ,dehydrothio-ptoluidine with m-toluylenediamine is ground to a suitable degree of fineness in a so-called colloid mill, and to the milled paste is added a dispersion of 200 ccs. cyclohexanol in 1 kilo of sodium sulphoricinoleate (50%). The whole is then diluted, with stirring, with boiling soft water, and filtered into a dyebath containing 300 litres of cold soft water. Dyeing is carried out exactly as in the previous example, the fabric being then lifted,

rinsed and dried or otherwise treated as requisite. J

Example!!! To dye 10 kilos of wool-cellulose acetate mixed goods in hank form} cellulose acetate yellow. wool red.

ratio wool: cellulose acetate 2:1

30 grams of the dyestufi obtained by diazotizing dehydrothio-p-toluidine and coupling with phenol are dispersed in 300 cos. of sodium sulphoricinoleate by the method described in Example ll, diluted with boiling water, and passed through a filter cloth into a dyebath containing 250 litres of soft water. The wool-cellulose acetate hanks are entered,

and dyeing commenced cold, the bath being heated to 7580 G. and dyeing continued till the requisite shade on the cellulose acetate is achieved. The goods are now lifted, rinsed and the wool dyed in a fresh bath of 250 litres volume containing 150 grams of A20 Rhodine 2G. (Colour Index No. 31.) Dyeing is' carried out at 80 C. with addition of 1 kilo of Glaubers salt, exhaustion being assistded by addition of 23% acetic or formic aci Tn a similar manner coloura tions may be obtained with unsulphonated thiazole derivatives on materials containing other organic substitution derivatives of cellulose, for example cellulose formate, cellulose butyrate, immunized cotton, or ethyl cellulose.

What we claim and desire to secure by Letters Patent is:

1. Process for coloring materials-comprising organic substitution products of cellulose,

comprising applying thereto unsulphonated thiaz'ole derivatives in which the dehydrothio-p-toluidine residue is linked through nitrogen to an aryl group.

'2. Process for coloring materials comprising cellulose esters comprising applying thereto unsulphonated thiazole derivatives in which the dehydro-thio-p-toluidine residue CH i S is linked through nitrogen to an aryl group.

, 3. Process for coloring materials comprising cellulose acetate, comprising applying thereto unsulphonated thiazole derivatives in which the dehydro-thio-p-toluidine residue f (lo o is linkedthrough nitrogen to an aryl group.

5. Materials comprising cellulose esters dyed with unsulphonated thiazole derivatives in which the dehydro-thio-p-toluidine residue is linked through nitrogen to a nitroaryl group.

In testimony whereof, subscribed our names.

GEORGE HOLLAND ELLIS. HENRYCHARLES OLPIN.'

we have hereunto is linked through nitrogen to an'aryl group. I I

'6.- Materials comprising cellulose acetate dyed with unsulphonated thiazole derivatives in which the dehydro-thio-p-toluidine residue cm s is linked through nitrogen to an aryl group. rocess for coloring materials compris- 1ng cellulose acetate, comprising applying thereto unsulphonated thiazole derivatives in which the dehydro-thio p-toluidine residue is linked through nitrogen to a' nitroaryl group. i

8. Materials comprising cellulose acetate dyed with unsulphonated thiazolederivatives in which the dehydro-thio-p-toluidine residue on s (EN c 

